Organoaluminosiloxane coating compositions and coated substrate

ABSTRACT

A method is provided for applying an aluminosilicate coating onto a substrate. For example, a superalloy is treated with an organic solvent solution of an aluminosiloxane having an Al/Si ratio having a value of 1 to 5 inclusive which is heated to an elevated temperature.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of application Ser. No. 625,412, filedJune 28, 1984, now U.S. Pat. No. 4,528,038, patented July 9, 1985.

Reference is made to the copending application of Leonard V. Interrante,Ser. No. 532,944, filed Sept. 16, 1983, now U.S. Pat. No. 4,460,654, forAluminosilicate Coating Method, Coated Articles and OrganosubstitutedSilicon-Oxygen-Aluminum Oligomers, assigned to the same assignee as thepresent invention.

BACKGROUND OF THE INVENTION

Prior to the present invention, it was generally known thataluminosilicate materials, for example, mullite, a naturally occurring,high temperature performing material composed essentially of chemicallycombined aluminum, oxygen and silicon atoms x(Al₂ O₃)SiO₂, where x is1.5 to 2.0, was an attractive candidate for a variety of hightemperature applications. In addition, mullite, unlike closely relatedaluminum-oxygen-silicon materials, is known to be highly resistant toattack by strong acids and other corrosive reagents, as taught by R. F.Davis and T. A. Pask, "Mullite", pp. 37-76 in "High Temperature Oxides",Part IV, Allen M. Alper, ed., Academic Press, NY (1971). However, notechnique was known for making mullite in a form such as a hightemperature, corrosion resistant, coating. It would be highly desirable,therefore, to provide a procedure whereby mullite could be madesynthetically in an appropriate form to utilize its outstandingproperties.

As shown by W.A.D.C. Technical Report, 58-160 ASTIA document No. 155675,The Air Force Inorganic Polymer Program, R. L. Rau (June 1958), Pages21-25, silicon-oxygen-aluminum polymers can be made by effectingreaction between an aluminum chelate dialkoxide, for example,diisopropoxyaluminum acetylacetonate and a difunctional silane, such asdimethylacetoxysilane. Reaction was carried out in boiling toluene toproduce a variety of products varying from soft resins, waxes, orpowders. It has been found that the aforementionedaluminum-oxygen-silicon materials of R. L. Rau provide glass-likecoatings when heated at temperatures exceeding 350° C. in an oxidizingatmosphere, for example air. However, the resulting aluminosilicatecoatings fall outside of the mullite compositions range, and do notprovide optimum coating characteristics on ceramic or metal substratesin particular applications. Additional procedures for makingorganoaluminosilanes are shown by S. N. Varisov et al, OrganosiliconHeteropolymers and Heterocompounds, Plenum Press, New York (1970).However, none of these procedures lead to the preparation oforganoaluminosilanes with Al/Si atomic ratios in the range appropriatefor mullite.

H. Dislich, New Routes to Multicomponent Oxide Glasses, AngewandteChemie, International Edition Vol. 10, pages 383-434 (1971) hasdescribed the preparation of coherent multicomponent oxide glasscoatings on various substrates using mixtures of metal alkoxides inorganic solvents. Similarly, Yoldas and Partlow, Formation of ContinuousBeta Alumina Films and Coatings at Low Temperatures, Ceramic Bulletin,Vol. 59, No. 6, (1980) pages 640-642, describe the preparation ofcontinuous films of NaAl₁₁ O₁₇ on ceramic substrates using solutions ofthe corresponding metal alkoxides. In both reports, removal of theorganic component is effected by hydrolysis of the organometallic filmafter deposition and the resultant metal oxide films do not possess thedesired thermal and chemical stability characteristic of mullite.

As shown by K. S. Mazdiyasni et al, Synthesis and Mechanical Propertiesof Stoichiometric Aluminum Silicate (Mullite), Pages 548,552, Vol. 55,No. 11, Journal of the American Ceramic Society, a method for preparingmullite is provided by reacting aluminum triisopropoxide and silicontetrakisisopropoxide under reflux conditions in isopropyl alcohol. Theresulting alkoxide solution can be ammoniated to produce thecorresponding hydroxy aluminosilicate which can be dried in vacuum toproduce mullite powders. However, the aforementioned technique wasunsuitable for applying a mullite coating onto various substrates.

Improved results have been obtained as shown by U.S. Pat. No. 4,434,103,Interrante, assigned to the same assignee as the present invention, whenchelated aluminum alkoxide of the formula ##STR1## where R is apolyvalent organic radical, Y is selected from a C.sub.(1-13) monovalenthydrocarbon radical and substituted C.sub.(1-13) monovalent hydrocarbonradical, and Z is selected from --O--, --S-- and --N═, were coreactedwith difunctional organosilane to produce an organic substitutedsilicon-oxygen-aluminum oligomer referred to hereinafter as the"organoaluminosiloxane". The organoaluminosiloxane was applied onto atemperature resistant substrate as an organic solvent solution which wastransformed into an aluminosilicate coating upon heating. Although theaforementioned method of Interrante provided valuable aluminosilicatecoatings on various substrates, it was often not possible to obtain aprecise control over the Al/Si ratio in the organoaluminosiloxane or theresulting aluminosilicate coating derived therefrom. This resulted in analuminosilicate coating providing a reduced degree of corrosionprotection. The degree of corrosion protection provided by analuminosilicate coating can be determined by the gain in weight of analuminosilicate coated sample subjected to a sodium sulfite-sulfurtrioxide atmosphere at 750° C. In addition, the use of a difunctionalsilane as a coreactant with the chelated aluminum alkoxide of formula(1) requires an initial prehydrolysis of such chelated aluminum alkoxidebefore the hydrolysis product can be coreacted with the difunctionalorganosilane.

The present invention is based on the discovery that organosilane havingthe formula,

    (R.sup.1).sub.a SiX.sub.4-a,                               (2)

where R¹ is selected from Y radicals as previously defined and "a" has avalue of about 2.5 to 3 inclusive, can be directly coreacted with achelated aluminum alkoxide of formula (1) in the presence of an organicsolvent to produce an organic solvent soluble organoaluminosiloxanehaving a predictable Al/Si ratio such as 3 to 1. In addition, theproduction of such organoaluminosiloxane in accordance with the practiceof the present invention does not require any prehydrolysis of thechelated aluminum alkoxide of formula (1) as required in the method ofInterrante, U.S. Pat. No. 4,434,103.

Although it is not completely understood why a predictable Al/Si ratiois feasible in the organoaluminosiloxane made in accordance with thepractice of the present invention, and not in accordance with the methodof U.S. Pat. No. 4,434,103, one possible explanation is that the use ofdifunctional silane results in the formation ofcyclopolydiorganosiloxane which readily separates from theorganoaluminosiloxane coating upon pyrolysis during the formation of thealuminosilicate coating.

STATEMENT OF THE INVENTION

There is provided by the present invention organoaluminosiloxane coatingcompositions comprising by weight

(A) 100 parts of an inert organic solvent, and

(B) 10 to 20 parts of an organoaluminosiloxane having an Al/Si ratiowhose value can vary between 1 to 5 inclusive consisting essentially ofchelated aluminum units of the formula ##STR2## chemically combined with(R¹)_(a) SiO.sub.(4-a)/2 units, where R, R¹, Z and a are as previouslydefined.

There is also included in the practice of the present invention, amethod for applying an aluminosilicate coating having a predictableAl/Si ratio onto a thermally insensitive substrate which comprises

(1) contacting the substrate with an organoaluminosiloxane coatingcomposition as defined above, in the substantial absence of moisture andeffecting the removal of solvent from the resulting treated substrate,

(2) heating the treated substrate in an oxidizing atmosphere to atemperature of 450° to 700° C. until an aluminosilicate coating isformed.

Chelated aluminum alkoxides of formula (1) which can be utilized in thepractice of the present invention are, for example ##STR3## where Y isselected from CH₃, C₂ H₆, C₃ H₇, etc., and R² is selected from H, CH₃,C₂ H₆, etc.

Organosilane of formula (2) which can be utilized in the practice of thepresent invention include, for example, monofunctional silanes such as##STR4##

In addition to the above trimethylsilanes, there can be usedorganohalosilanes, for example trimethylchlorosilane, which preferablyare used in combination with an HCl scavanger. In addition, there can beused mixtures of organosilanes, such as a mixturedimethyldiacetoxysilane and trimethyldiacetoxysilane having a ratio of2.5 to 3 R¹ radicals per silicon atom.

Radicals included within R of formula (1) are, for example, ##STR5## and--CH₂ CH₂ --. Radicals included within R¹ and Y of formulas (1) and (2)are for example, C.sub.(1-8) alkyl radicals, for example, methyl, ethyl,propyl, butyl, etc.; alkenyl radicals, for example, vinyl, propenyl,etc.; aryl radicals, for example phenyl, naphthyl, etc. Additional R¹radicals are for example, cyanoethyl and trifluoropropyl.

Temperature insensitive substrates which can be treated in accordancewith the practice of the method of the present invention are, forexample, fused silica, alumina, silicate glasses, titanium metal,inconel, tungsten carbide, superalloys, silicon, etc.

In the practice of the present invention, the organoaluminosiloxanecoating compositions of the present invention can be made by adding theorganosilane directly to the chelated aluminum alkoxide of formula (1)in the presence of an inert organic solvent, for example, a solvent freeof reactive --OH radicals, such as alcohols. Preferably, the addition isconducted under substantially anhydrous conditions. Suitable inertorganic solvents are, for example, benzene, toluene, chloroform,methylene chloride, acetone, ethers, etc. The organosilane is preferablyadded in the form of an organic solvent solution. The chelated aluminumalkoxide also can be utilized in the form of an organic solvent solutionduring the organosilane addition. Upon agitating the resulting mixture,the homogeneous solution can be brought to reflux temperature to effectthe separation of volatile side products and solvent until a highlyconcentrated product is obtained. Trace amounts of organic solvent andvolatiles can then be removed if desired from the resultingorganoaluminosiloxane by the employment of reduced pressure, such as0.02 to 0.10 torr, at ambient temperature.

A suitable temperature insensitive substrate such as a ceramicsubstrate, or superalloy substrate can then be treated with theorganoaluminosiloxane. Preferably, treatment is effected in thesubstantial absence of moisture to minimize hydrolysis of reactivemoisture sensitive functional group attached to silicon or aluminum. Thetreated substrate is preferably allowed to remain in an inert atmosphereto provide removal of organic solvent until a tack-free hard coating isformed. The coated substrate can thereafter be heated at a temperatureof from 450° C. to 700° C. in an oxidizing atmosphere for a timesufficient to oxidize any organic material on the treated substrate. Asuitable oxidizing atmosphere is, for example air, or an oxygencontaining gas or mixture thereof.

In order that those skilled in the art will be better able to practicethe present invention, the following examples are given by way ofillustration and not by way of limitation. All parts are by weight.

EXAMPLE 1

A solution of 4.356 g (0.033 moles) of trimethylacetoxysilane in 10 mlof benzene was added dropwise under substantially anhydrous conditionsto a stirred solution of 4.059 grams (0.0165 mole) ofbis(isopropoxy)acetylacetonate aluminum (3) in 20 ml of benzene. Thehomogeneous solution was brought to reflux temperature, where volatiles,side products and solvent were removed by distillation until a highlyconcentrated product was obtained. The remaining solvent and volatileside products were removed at ambient temperatures at 50 torr. Based onmethod of preparation, there was obtained an organoaluminosiloxanehaving the following average formula ##STR6## where n can have a valueof about 1 to 7.

The identity of the above product was further confirmed by elementalanalysis and GC and ¹ HNMR analysis. A 30% solution of theorganoaluminosiloxane was then prepared in toluene. A 2 cm×2 cm piece ofHastalloy C, nickelbased super alloy was dipped into theorganoaluminosiloxane solution under substantially anhydrous conditionsand the coated alloy was then heated to a temperature of 500° C. in airfor 180 minutes. There was obtained a Hastalloy C strip coated with auniform tough corrosion resistant aluminum silicate coating.

EXAMPLE 2

The procedure of Example 1 was repeated, except that a series oforganoaluminosiloxane coating compositions were prepared utilizingbis(isopropoxy)acetylacetonate aluminum and eithertrimethylacetoxysilane or dimethylacetoxysilane in benzene as a solvent.The proportions of the coreactants were varied to provide for theproduction of organoaluminosiloxane products having an Al/Si ratios overa range of from 1 to 5. Recovery of the various organoaluminosiloxanesusing the same stripping procedure as in Example 1 resulted in theproduction of various organoaluminosiloxanes which were analyzed foraluminum and silicon content by elemental analysis and GC and ¹ HNMRanalysis. The following results were obtained, where "A" representsorganoaluminosiloxane products which were made utilizingdimethyldiacetoxysilane, "B" represents organoaluminosiloxane productswhich were made utilizing trimethylacetoxysilane and "StartingMaterials" means the Al/Si ratio of the reactants used in the reactionmixture prior to stripping and "Products" means the Al/Si ratio afterstripping:

                  TABLE I                                                         ______________________________________                                        Starting                                                                      Materials         Products                                                    (Al/Si ratio)     A       B                                                   ______________________________________                                        1.0               3.07    1.04                                                2.0               3.62    2.02                                                3.0               3.76    3.12                                                4.0               4.61    4.07                                                5.0               11.46   5.10                                                ______________________________________                                    

The above results show that organoaluminosiloxanes prepared inaccordance with the practice of the present invention utilizingorganosilane having an average of from 2.5 to 3 R¹ radicals per siliconatom, provide organoaluminosiloxanes in which the Al/Si ratio isapproximately the same in the resulting organoaluminosiloxane asutilized in the initial reaction mixture. However, in instances wherethe starting organosilane have less than 2.5 R¹ radicals per siliconatom, such as dimethyldiacetoxysilane, a significant variation in theresulting organoaluminosiloxane with respect to the Al/Si ratio can beobtained as compared to the original Al/Si ratio utilized in theoriginal reaction mixture. One possible explanation is that thedimethyldiacetoxysilane used resulted in the production of cyclicpolysiloxanes which tended to self polymerize instead of coreact withthe bis(isopropoxy)acetylacetonate aluminum.

EXAMPLE 3

In accordance with the procedures of Examples 1 and 2 a series oforganoaluminosiloxane coating compositions were prepared from benzenesolutions of bis(isopropoxy)acetylacetonate aluminum and eithertrimethylacetoxysilane or dimethyldiacetoxysilane. The proportions ofthe silanes utilized with respect to the bis(isopropoxy)acetylacetonatewas sufficient to provide for an Al/Si ratio in the resultingorganoaluminosiloxane having a value of about 3. Coating compositionswere prepared from the respective organoaluminosiloxanes which were thenused to coat CoCrAlY test pins by dipping the pins into the respectivesolutions. The coated pins were then subjected to oxidation attemperatures in the range of between 1000° to 1500° C. for a period of 1hour to determine the ability of the resulting aluminosilicate coatingto resist oxidation which could be measured by measuring the gain inweight of the oxidized surface. Controls were also prepared of theCoCrAlY pins which were uncoated. The following results were obtainedwhere "A" represents aluminosilicate coated nickel alloy which was madeby oxidizing nickel alloy pins which had been treated withorganoaluminosiloxane derived from the use of dimethyldiacetoxysilaneand bis(isopropoxy)acetylacetonate aluminum. Nickel alloy pins treatedin accordance with the practice of the present invention resulting fromthe employment of organoaluminosiloxanes derived from the use oftrimethylacetoxysilane in accordance with the procedure of Example 1 areshown as "B". The following results were obtained:

                  TABLE 2                                                         ______________________________________                                                  Coating     Oxidation Weight Gain                                   Sample No.                                                                              Material    temp °(C.)                                                                       mg/cm.sup.2                                   ______________________________________                                        1         None        1000      0.5816                                        2         A           1000      0.4835                                        3         B           1000      0.1012                                        4         None        1500      1.2432                                        5         A           1500      0.9057                                        6         B           1500      0.2112                                        ______________________________________                                    

The above results show that the aluminosilicate coated pins made inaccordance with the practice of the present invention (B) have superiorcorrosion resistance as compared to pins which were not treated withorganoaluminosiloxane, or which were treated with organoaluminosiloxanemade from coreacting dimethyldiacetoxysilane andbis(isopropoxy)acetylacetonate aluminum (A).

Although the above examples are directed to only a few of the very manyvariables which can be utilized in the practice of the presentinvention, it should be understood that the present invention isdirected to a much broader variety of organoaluminosiloxanes and methodsfor making such materials and the use of such materials in coatingvarious substrates.

What I claim as new and desire to secure by Letters Patent of the UnitedStates:
 1. A method for applying an aluminosilicate coating having apredictable Al/Si ratio onto a substrate thermally insensitive totemperatures up to 1500° C. which comprises(1) contacting the substratewith an organic solvent solution of an organoaluminosiloxane andthereafter effecting the separation of organic solvent from the treatedsubstrate, (2) heating the treated substrate to a temperature of 450° to700° C. until an aluminosilicate coating is obtained,where the organicsolvent solution of an organoaluminosiloxane is a composition comprisingan organoaluminosiloxane coating compositions comprising by weight (A)100 parts of an inert organic solvent, and (B) 10 to 30 parts of anorganoalumoinosiloxane oligomer having an Al/Si ratio having a value of5 to 1 and consisting essentially of ##STR7## units chemically combinedwith (R¹)_(a) SiO.sub.(4-a)/2 units where R is a polyvalent organicradical, R¹ is selected from a C.sub.(1-13) monovalent hydrocarbonradical and substituted C.sub.(1-13) monovalent hydrocarbon radical, Zis selected from --O--, --S-- and --N═, and a has a value of 2.5 to 3.2. A method for making an organoaluminosiloxane having an Al/Si ratio of1 to 5, which comprises(1) effecting reaction between a chelatedaluminum alkoxide of the formula, ##STR8## and organosilane of theformula,

    (R.sup.1).sub.a SiX.sub.4-a

in the presence of an organic solvent, (2) stripping the resultingmixture of (1) of volatiles at a temperature up to 120° C.,where R is apolyvalent organic radical, R¹ is selected from a C.sub.(1-13)monovalent hydrocarbon radical and substituted C.sub.(1-13) monovalenthydrocarbon radical, Z is selected from --O--, --S-- and --N═, and has avalue of 2.5 to
 3. 3. A method in accordance with claim 2, where thealuminum alkoxide is bis(isopropoxy)acetylacetonate aluminum (III) andthe organosilane is trimethylacyloxysilane.